CN113632189B - Electrolytic capacitor and method for manufacturing the same - Google Patents

Electrolytic capacitor and method for manufacturing the same Download PDF

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Publication number
CN113632189B
CN113632189B CN202080024652.2A CN202080024652A CN113632189B CN 113632189 B CN113632189 B CN 113632189B CN 202080024652 A CN202080024652 A CN 202080024652A CN 113632189 B CN113632189 B CN 113632189B
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anode body
layer
surface layer
porosity
electrolytic capacitor
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CN113632189A (en
Inventor
大形德彦
矢野佑磨
后藤和秀
杉原之康
凤桐将之
上田政弘
小田根和仁
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0036—Formation of the solid electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/008—Terminals
    • H01G9/012—Terminals specially adapted for solid capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/025—Solid electrolytes
    • H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/14—Structural combinations or circuits for modifying, or compensating for, electric characteristics of electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15—Solid electrolytic capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052—Sintered electrodes
    • H01G9/0525—Powder therefor

Abstract

The electrolytic capacitor (20) is provided with a capacitor element (10), wherein the capacitor element (10) comprises a porous anode body (1), a dielectric layer (3) formed on the surface of the anode body (1), and a solid electrolyte layer (4) covering at least a part of the dielectric layer (3). The anode body (1) has a plurality of main surfaces, and corner portions including a plurality of side portions connecting the plurality of main surfaces to each other and 1 or more vertex portions connecting the plurality of main surfaces to each other. The surface layer X of at least a part of the corner portion is denser than the surface layer Y of the main surface adjacent to the surface layer X.

Description

Electrolytic capacitor and method for manufacturing the same
Technical Field
The present invention relates to an electrolytic capacitor and a method for manufacturing the same.
Background
Electrolytic capacitors have low Equivalent Series Resistance (ESR) and excellent frequency characteristics, and are therefore mounted in various electronic devices. Electrolytic capacitors generally include a capacitor element having an anode portion and a cathode portion. The anode portion includes a porous anode body, and a dielectric layer is formed on the surface of the anode body. The dielectric layer is in contact with the electrolyte. There is an electrolytic capacitor using a solid electrolyte such as a conductive polymer as an electrolyte (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-182157
Disclosure of Invention
Problems to be solved by the invention
The reliability of an electrolytic capacitor using a solid electrolyte is improved.
Means for solving the problems
An aspect of the present invention relates to an electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the anode body including a plurality of principal surfaces, and corner portions including a plurality of edge portions and a vertex portion connecting the plurality of principal surfaces to each other, a surface layer X of at least a part of the corner portions being denser than a surface layer Y of the principal surface adjacent to the surface layer X.
Another aspect of the present invention relates to a method for manufacturing a solid electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the method comprising: preparing the anode body; covering at least a part of the anode body with the dielectric layer; and a step of covering at least a part of the dielectric layer with the solid electrolyte layer, wherein the anode body has a plurality of main surfaces and corner portions including a plurality of side portions and vertex portions connecting the plurality of main surfaces to each other, and the step of preparing the anode body includes a step of irradiating at least a part of the corner portions with laser light.
A further aspect of the present invention relates to a method for manufacturing a solid electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the method comprising: preparing the anode body; covering at least a part of the anode body with the dielectric layer; and a step of covering at least a part of the dielectric layer with the solid electrolyte layer, wherein the anode body has a plurality of main surfaces and corner portions including edge portions and vertex portions connecting the plurality of main surfaces to each other, and the step of preparing the anode body includes a step of causing dielectric particles to collide with at least a part of the corner portions.
A further aspect of the present invention relates to a method for manufacturing a solid electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the method comprising: preparing the anode body; covering at least a part of the anode body with the dielectric layer; and a step of covering at least a part of the dielectric layer with the solid electrolyte layer, wherein the anode body has a plurality of main surfaces, and corner portions including edge portions and vertex portions connecting the plurality of main surfaces to each other, and the step of preparing the anode body includes a step of vibrating the anode body together with a vibrating member.
Effects of the invention
The reliability of the electrolytic capacitor is improved.
The novel features of the invention, both as to its organization and content, together with further objects and features of the invention will be better understood by reference to the following detailed description when considered in connection with the accompanying drawings.
Drawings
Fig. 1 is a perspective view schematically showing the shape of an anode body used in an electrolytic capacitor according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view schematically showing an electrolytic capacitor according to an embodiment of the present invention.
Fig. 3 is an electron micrograph of a cross section of a corner portion of the anode body after laser irradiation.
Detailed Description
[ electrolytic capacitor ]
An electrolytic capacitor according to one embodiment of the present invention includes a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer. The anode body has a plurality of main faces and corner portions. The corner portion includes, for example, a plurality of edge portions connecting the plurality of main faces to each other, and 1 or more vertex portions connecting the plurality of main faces to each other. At least a portion of the corner portion has a curved surface or is chamfered.
In the anode body, by providing a curved surface or chamfering at least a part of the side portion and/or the apex portion, damage of the dielectric layer in the corner portion is suppressed, and an electrolytic capacitor with a small leakage current can be realized. Therefore, the reliability of the electrolytic capacitor can be improved.
The side portion is a region where the 2 main surfaces of the anode element intersect and the vicinity thereof. The vertex portion refers to the vertex at which the 3 main faces of the anode body intersect and the region in the vicinity thereof. The edge portions and the vertex portions are collectively referred to herein as "corner portions". At least a part of the corner portions have a curved surface or are chamfered, meaning that for example at least one edge portion and/or at least one vertex portion has a curved surface or are chamfered. In addition, a case where a part of one side portion has a curved surface or is chamfered is included.
In addition, the fact that at least a part of the corner portion has a "curved surface" is not limited to the case where the cross-sectional shape of the corner portion is curved. For example, the cross-sectional shape of the corner portion may be a broken line having a plurality of obtuse angles. When the cross-sectional shape is convex and a straight line corresponding to one main surface and a straight line corresponding to the other adjacent main surface are connected via at least one straight line and/or curved line, the corner portion can be said to have a curved surface. In other words, having a "curved surface" in the corner portion also means: in the cross-sectional shape of the corner portion in the cross-section perpendicular to the adjacent 2 main faces, a sharp region of 90 ° or less is not present.
The dielectric layer is generally formed by subjecting an anode body to a chemical conversion treatment to grow an oxide film on the surface of the anode body. Therefore, the properties of the dielectric layer formed by chemical conversion are affected by the surface state of the anode body before the chemical conversion treatment.
The anode body typically has the shape of a cuboid. In this case, the surface of the anode body is uneven when viewed microscopically in the vicinity of the side connecting the 2 orthogonal principal surfaces of the rectangular parallelepiped and/or in the vicinity of the vertex (corner portion) where the 3 mutually orthogonal principal surfaces of the rectangular parallelepiped intersect, and the surface roughness is large, and is likely to have a concave-convex shape. If the dielectric layer is grown by chemical conversion treatment in this state, defects are likely to occur in the dielectric layer in the concave-convex portion. If defects are generated in the dielectric layer, the following is present: a path through which current flows between the solid electrolyte and the valve action metal via the defective portion is generated, and leakage current increases.
In addition, the anode body is porous, and therefore, is fragile and easily damaged. In particular, the corner portions of the anode body have lower mechanical strength and thermal stress is easily concentrated than portions other than the corner portions. The following situations exist: since the porous portion is damaged, the dielectric layer covering the porous portion is damaged. There are cases where leakage current increases due to damage to the dielectric layer.
In the electrolytic capacitor according to the present embodiment, at least a part of the corner portion of the anode body is formed into a curved surface in advance, so that defects in chemical conversion of the dielectric layer can be reduced. As a result, leakage current can be reduced. In addition, mechanical strength can be improved and thermal stress can be relaxed. This can suppress damage to the dielectric layer after chemical conversion. As a result, an increase in leakage current can be suppressed.
The solid electrolyte layer is formed so as to cover the dielectric layer. In the case where the corner portion of the anode body does not have a curved surface, the thickness of the solid electrolyte layer at the corner portion is easily formed thin. In particular, when the solid electrolyte layer contains a conductive polymer and the conductive polymer is formed by chemical polymerization, the thickness of the solid electrolyte layer tends to be thin in the corner portion. However, by forming at least a part of the corner portion into a curved surface, thinning of the solid electrolyte layer at the corner portion can be suppressed, and the solid electrolyte layer can be formed with a uniform thickness. This makes it possible to suppress an increase in leakage current and occurrence of short-circuit failure, by making the electrolytic capacitor stronger against stress from the outside. In addition, withstand voltage increases.
The surface layer X of at least a part of the corner portion may be denser than the surface layer Y of the main surface adjacent to the surface layer X. The surface layer Y is a surface layer of the main surface adjacent to the corner portion, and the porous anode body is exposed. By densely forming the surface layer X at the corner portion, the mechanical strength of the corner portion can be further improved. Therefore, the suppression effect on the increase of the leakage current through the corner portion can be improved.
In addition, in the case where at least a part of the surface layer X of the angled portion is densely formed, the dense surface layer X may not be a curved surface or may not be a chamfered surface layer. Even in the case where the corner portion does not have a curved surface and is not chamfered, sufficient mechanical strength can be obtained by densely forming the surface layer X of the corner portion. Therefore, an increase in leakage current through the corner portion can be suppressed. However, if at least a part of the portion including the surface layer X is in a curved shape or a chamfer shape, leakage current can be further suppressed, which is preferable. In this case, the surface layer Y may be a region adjacent to a portion of the surface layer X having a curved shape or a chamfer shape.
The densification of the surface layer X with respect to the surface layer Y means, for example, the porosity P in the surface layer X 1 Less than the porosity P in the surface layer Y 2 . The surface layer X may have, for example, a porosity P 1 A content of 10% or less. In contrast, the porosity P in the surface layer Y 2 Typically 20% or more.
The surface layers X and Y may have a porosity P 2 Relative to the porosity P 1 Ratio P of 2 /P 1 For example, a fraction of 5 or more is satisfied. P (P) 2 /P 1 May be 10 or more or 50 or more. Any portion of the surface layer X and any portion of the surface layer Y can satisfy P 2 /P 1 Is 5 or more.
In the case where at least a part of the corner portion has a curved surface, the curvature of the curved surface is, for example, 0.002 (1/μm) to 0.05 (1/μm), and more preferably 0.005 (1/μm) to 0.02 (1/μm).
The curvature and porosity are obtained by image analysis of a cross-sectional photograph of the anode body in a predetermined region. In the electron micrograph of the cross section, the area of the void portion in any region A in the surface layer X was obtained, and the ratio of the area of the void portion to the region A was defined as the porosity P 1 . Similarly, the area of the void portion in any region B in the surface layer Y is obtained, and the ratio of the area of the void portion to the region B is defined as the porosity P 2 。
The corner portions having the curved surfaces may be formed by press molding the anode body using a mold in which the curved surfaces are formed, or may be formed by removing a part of the corner portions of the anode body. However, by irradiating laser to the diagonal portion, a curved surface and/or a surface layer in which the diagonal portion is densely formed can be formed. The surface layer X of the corner portion is melted by irradiation of laser light. The surface layer X after laser irradiation is a molten layer formed by melting the porous portion of the anode body, and can be formed more densely than the porous surface layer Y. The porosity P of the surface layer X formed by laser irradiation 1 The minimum value may be, for example, 1% or less.
Alternatively, the anode body may be placed on a vibrating member such as a screen or a dielectric particle, and the vibrating member may be vibrated to form the corner portion into a curved surface. In this case, the corner portions of the anode body collide with the vibration member due to vibration, the corner portions are compressed due to the collision, and the corner portions can be formed in a curved shape. This can form the surface layer X at the corner portion more densely (with a higher density) than the surface layer Y of the main surface of the porous material.
The corner portion includes a portion having a curvature radius R of 20 μm to 500 μm, and more preferably includes a portion having a curvature radius R of 50 μm to 200 μm. Here, the radius of curvature of the corner portion is calculated by taking a photograph of the anode body from one principal surface side and performing image analysis on the contour shape in the vicinity of the corner portion (vertex) obtained. In the contour line of the anode body, the distance from the boundary between the region where the curved surface is formed (chamfered portion) and the side portion where the curved surface is not formed (not chamfered) to the vertex position before the curved surface is formed (position of intersection of the side portion and the side portion) is obtained and regarded as the radius of curvature R. The radius of curvature R may be calculated for each side portion of the anode body, and an average value may be calculated. For example, when the anode body is substantially rectangular, the radii of curvature R are obtained at both ends of 12 side portions, and an average value of 24 radii of curvature R in total is obtained. By using the vibrating member, an anode body having an average value of the radius of curvature R in the above range is easily obtained.
In the corner portions of the anode body, the portions having the curved surface shape or the chamfer shape may include portions having the above-described radii of curvature R different from each other. In this case, the variation in the radius of curvature R of the plurality of corner portions in the anode body may be, for example, 350 μm or less, and more preferably 150 μm or less. The deviation of the radius of curvature R is the difference between the maximum value and the minimum value of the radius of curvature R of the corner portion calculated by the above method (the difference between the maximum value and the minimum value of the 24 calculated radii of curvature in the case where the anode body is a substantially rectangular parallelepiped).
Fig. 1 is a schematic perspective view showing an example of an anode body used in the electrolytic capacitor of the present embodiment. As shown in fig. 1, the anode element 1 has a substantially rectangular parallelepiped shape, and 6 main surfaces 101A to 101F are exposed. Further, 101D to 101F are located at positions hidden from the paper surface, and are not shown.
In the main surfaces 101A to 101F, a connecting surface is formed by removing corners of side portions in the vicinity of sides where two adjacent main surfaces intersect with each other. In the example of fig. 1, the connection surface 102C is interposed between the main surfaces 101A and 101B, the connection surface 102A is interposed between the main surfaces 101B and 101C, and the connection surface 102A is interposed between the main surfaces 101B and 101C. In addition, a second connection surface is formed by removing the corners of the vertex portion in the vicinity of the vertex where the 3 main surfaces intersect. In the example of fig. 1, the second connection surface 103A is provided at the vertex portion where the main surfaces 101A to 101C intersect. The second connection surface 103A connects the connection surfaces 102A to 102C to each other. The connection surfaces 102A to 102C and the second connection surface 103A are machined into curved surfaces with rounded corners. The connection surfaces 102A to 102C and the second connection surface 103A may be curved surfaces or may be formed of one or more flat surfaces (for example, corner portions may be chamfered).
By forming the anode element 1 in such a shape that the sharp portion is removed, a dielectric layer with few defects can be formed on the surface of the anode element 1. As a result, leakage current can be reduced. In addition, the mechanical strength of the anode body is improved, and the concentration of thermal stress is relaxed. As a result, damage to the dielectric layer can be suppressed, an increase in leakage current due to damage to the dielectric layer can be suppressed, and the leakage current can be kept small.
The surface layers of the connection surfaces 102A to 102C and/or the second connection surface 103A may be formed denser than the surface layers of the porous main surfaces 101A to 101F. That is, the porosity P in the surface layers of the connection surfaces 102A to 102C and/or the second connection surface 103A 1 May be smaller than the porosity P in the surface layer of the main surfaces 101A to 101F 2 . In this case, the mechanical strength of the corner portion of the anode body can be further improved.
The anode wire 2 extends from the main surface 101B of the anode body 1. The anode body 1 and the anode wire 2 constitute an anode portion 6.
Hereinafter, the structure of the electrolytic capacitor according to the present embodiment will be described with reference to the drawings. However, the present invention is not limited thereto. Fig. 2 is a schematic cross-sectional view of the electrolytic capacitor of the present embodiment.
The electrolytic capacitor 20 includes: the capacitor element 10 includes the anode portion 6 and the cathode portion 7, the exterior body 11 sealing the capacitor element 10, the anode lead terminal 13 electrically connected to the anode portion 6 and partially exposed from the exterior body 11, and the cathode lead terminal 14 electrically connected to the cathode portion 7 and partially exposed from the exterior body 11. The anode portion 6 has an anode body 1 and an anode wire 2. A dielectric layer 3 is formed on the surface of the anode body. The cathode portion 7 has a solid electrolyte layer 4 covering at least a part of the dielectric layer 3 and a cathode layer 5 covering the surface of the solid electrolyte layer 4.
< capacitor element >
Hereinafter, the capacitor element 10 will be described in detail with reference to the case of providing a solid electrolyte layer as an electrolyte.
The anode portion 6 includes an anode body 1 and an anode wire 2 extending from one surface of the anode body 1 and electrically connected to an anode lead terminal 13.
The anode body 1 is, for example, a rectangular parallelepiped porous sintered body obtained by sintering metal particles. As the metal particles, particles of valve metal such as titanium (Ti), tantalum (Ta), and niobium (Nb) are used. The anode body 1 may use 1 or 2 or more kinds of metal particles. The metal particles may be an alloy composed of 2 or more metals. For example, alloys containing valve action metals and silicon, vanadium, boron, etc. may be used. In addition, a compound containing a typical element such as a valve metal and nitrogen may be used. The valve metal alloy contains a valve metal as a main component, for example, 50 atomic% or more of the valve metal.
The anode wire 2 is made of a conductive material. The material of the anode wire 2 is not particularly limited, and examples thereof include copper, aluminum alloy, and the like, in addition to the valve metal. The anode body 1 and the anode wire 2 may be made of the same material or different materials. The anode wire 2 has: a first portion 2a buried in the anode body 1 from one surface of the anode body 1, and a second portion 2b extending from the one surface of the anode body 1. The cross-sectional shape of the anode wire 2 is not particularly limited, and examples thereof include a circular shape, an endless belt shape (a shape composed of straight lines parallel to each other and 2 curved lines connecting end portions of the straight lines to each other), an elliptical shape, a rectangular shape, a polygonal shape, and the like.
The anode portion 6 is produced, for example, by press-forming a rectangular parallelepiped shape in a state where the first portion 2a is embedded in the powder of the metal particles, and sintering the rectangular parallelepiped shape. Thereby, the second portion 2b of the anode wire 2 is led out from one side of the anode body 1 in an extended manner. The second portion 2b is joined to the anode lead terminal 13 by welding or the like, and the anode wire 2 is electrically connected to the anode lead terminal 13. The welding method is not particularly limited, and examples thereof include resistance welding and laser welding. Thereafter, a process of forming a curved surface at the corner portion of the rectangular parallelepiped can be performed.
A dielectric layer 3 is formed on the surface of the anode body 1. The dielectric layer 3 is made of, for example, metal oxide. Examples of the method of forming the metal oxide-containing layer on the surface of the anode body 1 include a method of immersing the anode body 1 in a chemical conversion solution to anodize the surface of the anode body 1 and a method of heating the anode body 1 in an atmosphere containing oxygen. The dielectric layer 3 is not limited to a layer containing the metal oxide, and may be insulating.
(cathode portion)
The cathode portion 7 has a solid electrolyte layer 4 and a cathode layer 5 covering the solid electrolyte layer 4. The solid electrolyte layer 4 is formed so as to cover at least a part of the dielectric layer 3.
The solid electrolyte layer 4 is made of, for example, a manganese compound or a conductive polymer. Examples of the conductive polymer include polypyrrole, polythiophene, polyfuran, polyaniline, and polyacetylene. These may be used alone or in combination. The conductive polymer may be a copolymer of 2 or more monomers. From the viewpoint of excellent conductivity, polythiophene, polyaniline, and polypyrrole can be used. In particular, polypyrrole may be used in view of excellent hydrophobicity.
The solid electrolyte layer 4 containing the conductive polymer is formed, for example, by polymerizing a raw material monomer on the dielectric layer 3. Alternatively, the conductive polymer is formed by applying a liquid containing the conductive polymer to the dielectric layer 3. The solid electrolyte layer 4 is composed of 1 or 2 or more solid electrolyte layers. When the solid electrolyte layer 4 is composed of 2 or more layers, the composition, formation method (polymerization method), and the like of the conductive polymer used in each layer may be different.
In the present specification, polypyrrole, polythiophene, polyfuran, polyaniline, and the like refer to polymers having polypyrrole, polythiophene, polyfuran, polyaniline, and the like as basic backbones, respectively. Accordingly, the polypyrrole, polythiophene, polyfuran, polyaniline, and the like may contain the respective derivatives. For example, polythiophenes include poly (3, 4-ethylenedioxythiophene) and the like.
To the polymerization solution, solution or dispersion for forming the conductive polymer, various dopants may be added in order to improve the conductivity of the conductive polymer. The dopant is not particularly limited, and examples thereof include naphthalene sulfonic acid, p-toluene sulfonic acid, polystyrene sulfonic acid, and the like.
When the conductive polymer is dispersed in the dispersion medium in the form of particles, the average particle diameter D50 of the particles is, for example, 0.01 μm or more and 0.5 μm or less. If the average particle diameter D50 of the particles is within this range, the particles easily intrude into the anode body 1.
The cathode layer 5 includes, for example, a carbon layer 5a formed so as to cover the solid electrolyte layer 4, and a metal paste layer 5b formed on the surface of the carbon layer 5 a. The carbon layer 5a contains a conductive carbon material such as graphite and a resin. The metal paste layer 5b contains, for example, metal particles (e.g., silver) and a resin. The structure of the cathode layer 5 is not limited to this structure. The cathode layer 5 may be formed so as to have a current collecting function.
< anode lead terminal >
The anode lead terminal 13 is electrically connected to the anode body 1 via the second portion 2b of the anode wire 2. The material of the anode lead terminal 13 is not particularly limited as long as it is electrochemically and chemically stable and has conductivity. The anode lead terminal 13 may be made of a metal such as copper, or may be made of a nonmetal. The shape is not particularly limited as long as it is a flat plate. From the viewpoint of thickness reduction, the thickness of the anode lead terminal 13 (the distance between the main surfaces of the anode lead terminal 13) may be 25 μm or more and 200 μm or less, or may be 25 μm or more and 100 μm or less.
One end of the anode lead terminal 13 may be joined to the anode wire 2 by a conductive adhesive or solder, or may be joined to the anode wire 2 by resistance welding or laser welding. The other end of the anode lead terminal 13 is led out of the exterior body 11, and is exposed from the exterior body 11. The conductive adhesive is, for example, a mixture of a thermosetting resin, carbon particles, and metal particles, which will be described later.
< cathode lead terminal >
The cathode lead terminal 14 is electrically connected to the cathode portion 7 at the joint portion 14 a. The joint 14a is a portion of the cathode lead terminal 14 overlapping the cathode layer 5 when the cathode layer 5 and the cathode lead terminal 14 joined to the cathode layer 5 are viewed from the normal direction of the cathode layer 5.
The cathode lead terminal 14 is bonded to the cathode layer 5 via, for example, the conductive adhesive 8. One end of the cathode lead terminal 14 constitutes, for example, a part of the joint portion 14a, and is disposed inside the exterior body 11. The other end of the cathode lead terminal 14 is led out. Therefore, a part of the cathode lead terminal 14 including the other end portion is exposed from the exterior body 11.
The material of the cathode lead terminal 14 is not particularly limited as long as it is electrochemically and chemically stable and has conductivity. The cathode lead terminal 14 may be made of a metal such as copper, or may be made of a nonmetal. The shape is also not particularly limited, and is, for example, a long and flat plate shape. From the viewpoint of thickness reduction, the thickness of the cathode lead terminal 14 may be 25 μm or more and 200 μm or less, or may be 25 μm or more and 100 μm or less.
< outer body >
The exterior body 11 is provided for electrically insulating the anode lead terminal 13 and the cathode lead terminal 14, and is made of an insulating material (exterior body material). The exterior body material includes, for example, a thermosetting resin. Examples of the thermosetting resin include epoxy resin, phenolic resin, silicone resin, melamine resin, urea resin, alkyd resin, polyurethane, polyimide, and unsaturated polyester.
Method for manufacturing electrolytic capacitor
An example of the method for manufacturing an electrolytic capacitor according to the present embodiment will be described below.
The method for manufacturing an electrolytic capacitor includes a step of preparing an anode body, a step of covering at least a part of the anode body with a dielectric layer, and a step of covering at least a part of the dielectric layer, wherein the anode body has a plurality of main surfaces and corner portions including a plurality of edge portions and vertex portions connecting the plurality of main surfaces to each other, and the step of preparing the anode body has a step of forming a curved surface in at least a part of the corner portions or chamfering at least a part of the corner portions.
(1) Preparation step of anode body
As the anode body 1, a porous sintered body can be used. The valve metal particles and the anode wire 2 are placed in a mold so that the first portion 2a is embedded in the valve metal particles, press-molded, and then sintered to obtain the anode portion 6 of the anode body 1 including the porous body of the valve metal. The first portion 2a of the anode wire is buried in the porous sintered body from one surface thereof. The pressure at the time of press molding is not particularly limited. The sintering is preferably carried out under reduced pressure. If necessary, a binder such as a polyacrylic acid carbonate may be mixed with the valve metal particles.
The valve metal particles are usually press-molded and sintered using a mold having a rectangular parallelepiped internal space. In this case, the sintered anode element 1 is also rectangular in shape and has a plurality of main surfaces. In this case, the plurality of main surfaces are directly connected to each other to form a side and a vertex, and the tip end portion of the side portion and/or the vertex portion, i.e., the corner portion connecting the plurality of main surfaces to each other is pointed.
The anode body having the sharp distal end portion may be subjected to a process of forming a curved surface in at least a part of the corner portion or a process of chamfering at least a part of the corner portion. Thereby, the corners of the tip portion are removed, and for example, the tip portion can be processed into a rounded shape. The processing for forming the curved surface in the corner portion may be performed by, for example, removing a part of the corner portion and removing the tip portion.
In the machining step of forming a curved surface at least a part of the corner portion or chamfering at least a part of the corner portion, at least a part of the corner portion can be formed at a high density. For example, by irradiating laser to the corner portions, the corner portions are formed into curved surfaces, and at least a part of the corner portions can be formed with high density. Alternatively, the anode body may be vibrated together with the vibration member. Along with the vibration, particularly the corner portion of the anode body collides with the vibration member, the corner portion is compressed, thereby forming a curved surface, and at least a part of the corner portion can be formed with high density.
The curved surface may be formed in the corner portion by irradiating the corner portion with laser light. By irradiating the corner portion with laser light, the corner portion is melted, and the tip portion can be changed from a sharp shape to a shape having a curved surface. The molten layer formed after the melting is denser than the porous portion of the anode body, and has extremely small porosity. Therefore, the mechanical strength of the corner portion can be remarkably improved, and the damage suppressing effect of the dielectric layer at the corner portion is large. The thickness of the molten layer may be, for example, 1 μm to 100. Mu.m.
The laser used for the laser irradiation is not limited, and for example, a YAG (Yttrium Aluminum Garnet: yttrium aluminum garnet) laser (wavelength 1064 nm) may be used.
In forming the solid electrolyte layer, it is preferable to irradiate the diagonal portion with laser light and not substantially irradiate the main surface of the anode body adjacent to the diagonal portion, from the viewpoint that air existing in the pores of the anode body is easily discharged. The above description refers to a case where a laser beam is not irradiated to a large part of the main surface, and irradiation of a laser beam to a part of the main surface (for example, a region on the main surface adjacent to the corner portion) is not excluded.
The irradiation with the laser light may be performed on the anode body after sintering, or may be performed on the valve metal particles before sintering, which are press-molded. However, if the deformation associated with the volume shrinkage after sintering is taken into consideration, it is preferable to irradiate the sintered anode body with laser light.
In the case of vibrating the anode body together with the vibrating member, for example, the tip end portion can be removed by placing the anode body on a base (vibrating member) having irregularities on the surface, such as a screen (sieve) or a file, and vibrating the base in the up-down direction and/or the left-right direction. With the vibration of the base, the anode body rolls and moves on the base while jumping. With this, a part of the front end portion of the corner portion is shaved off, and a curved surface is formed in the corner portion. However, most of the distal end portion can remain in the surface layer of the corner portion in a compressed state without being shaved off. As a result, the surface layer having the corner portion of the curved surface can be formed at high density. The screen may be used for the base, since the residue scraped off from the tip end portion is likely to fall downward and be removed, and the static friction coefficient is moderately small and the anode body is likely to be rolled and moved. The mesh of the screen is less than the minimum value of the outer diameter of the anode body so that the anode body does not fall through the openings of the screen. The mesh size of the screen may be 1mm or more, or may be 2mm or more and 3.4mm or less. If the mesh size is 1mm or more, the variation in the radius of curvature R of the corner portion is easily reduced to a certain value or less.
The anode element may be vibrated together with the dielectric particles by applying an external force to the dielectric particles in a state where the anode element is placed on the dielectric particles. For example, the anode body and the dielectric particles may be mixed, and the anode body and the dielectric particles may be put into an oscillator together, and the oscillator may be operated. The oscillator is preferably capable of applying vibration in a vertical direction in addition to vibration in a horizontal direction. As the medium particles, alumina particles, zirconia particles, or the like can be used. The medium particles may have a particle diameter (average particle diameter) of, for example, 0.1mm to 3mm or 0.5mm to 2mm.
The dielectric particles put into the oscillator together with the anode body vibrate by the operation of the oscillator, and collide with the anode body. The corner portions of the anode body are susceptible to deformation by collision because of low mechanical strength, and the porous portions of the corner portions are susceptible to crushing and compression. Therefore, the surface layer of the angled portion can be formed at high density.
The density of the medium particles may be 0.15 to 0.4 times the density (true density) of the anode body. In the case where the density of the medium particles is in the above range, energy generated by collision of the medium particles can be effectively used for compression deformation of the corner portions. In addition, the ratio of the corner portions to be shaved off by the collision can be reduced.
In the method of vibrating the medium particles in a state where the anode body and the medium particles are mixed, a curved surface can be formed or chamfering can be performed in a corner portion in a shorter time than in the method of vibrating a screen on which the anode body is mounted. Therefore, the deviation of the radius of curvature R at the corner portion is easily reduced.
In the case of forming or chamfering the curved surface of the corner portion using the vibration member, it is preferable to form or chamfer the curved surface of the corner portion of the porous body before sintering because the mechanical strength is improved by sintering, and the corner portion is difficult to compress.
The valve metal particles are pressed and molded using a die having the corners removed in advance, and sintered, whereby an anode body having curved surfaces formed at the corner portions can be obtained.
(2) Dielectric layer forming step
Next, the anode body 1 is subjected to a chemical conversion treatment, and at least a part of the anode body 1 is covered with the dielectric layer 3. Specifically, the anode body 1 is immersed in a chemical conversion tank filled with an electrolytic aqueous solution (for example, an aqueous phosphoric acid solution), and the second portion 2b of the anode wire 2 is connected to the anode body of the chemical conversion tank, and anodic oxidation is performed, whereby the dielectric layer 3 composed of the oxide film of the valve metal can be formed on the surface of the porous portion. The electrolytic aqueous solution is not limited to the phosphoric acid aqueous solution, and nitric acid, acetic acid, sulfuric acid, and the like may be used.
(3) Process for forming solid electrolyte layer
Next, at least a part of the dielectric layer 3 is covered with the solid electrolyte layer 4. Thus, the capacitor element 10 including the anode body 1, the dielectric layer 3, and the solid electrolyte layer 4 was obtained.
The solid electrolyte layer 4 containing a conductive polymer is formed on at least a part of the dielectric layer 3 by, for example, a method of impregnating the anode body 1 on which the dielectric layer 3 is formed with a monomer or an oligomer, and then polymerizing the monomer or the oligomer by chemical polymerization or electrolytic polymerization, or a method of impregnating the anode body 1 on which the dielectric layer 3 is formed with a solution or dispersion of a conductive polymer and drying the solution or dispersion.
The solid electrolyte layer 4 may be formed, for example, by impregnating the anode body 1 having the dielectric layer 3 formed therein with a dispersion liquid containing a conductive polymer, a binder and a dispersion medium, taking out the dispersion liquid, and drying the dispersion liquid. The dispersion may contain a binder and/or conductive inorganic particles (e.g., a conductive carbon material such as carbon black). The conductive polymer may contain a dopant. The conductive polymer and the dopant may be selected from the materials exemplified for the solid electrolyte layer 4. The binder may be a known binder. The dispersion may contain known additives used in forming the solid electrolyte layer.
Next, the carbon paste and the metal paste are sequentially applied to the surface of the solid electrolyte layer 4, thereby forming a cathode layer 5 composed of a carbon layer 5a and a metal paste layer 5b. The structure of the cathode layer 5 is not limited to this, and may be one having a current collecting function.
Next, the anode lead terminal 13 and the cathode lead terminal 14 are prepared. The second portion 2b of the anode wire 2 extending from the anode body 1 is joined to the anode lead terminal 13 by laser welding, resistance welding, or the like. After the conductive adhesive 8 is applied to the cathode layer 5, the cathode lead terminal 14 is bonded to the cathode portion 7 via the conductive adhesive 8.
Next, the capacitor element 10 and the material of the exterior body 11 (for example, uncured thermosetting resin and filler) are accommodated in a mold, and the capacitor element 10 is sealed by a transfer molding method, a compression molding method, or the like. At this time, a part of the anode lead terminal 13 and the cathode lead terminal 14 is exposed from the mold. The molding conditions are not particularly limited, and the time and temperature conditions may be appropriately set in consideration of the curing temperature of the thermosetting resin used, and the like.
Finally, the exposed portions of the anode lead terminal 13 and the cathode lead terminal 14 are bent along the exterior body 11 to form bent portions. Thus, a part of the anode lead terminal 13 and the cathode lead terminal 14 is placed on the mounting surface of the package 11.
The electrolytic capacitor 20 is manufactured by the above method.
Fig. 3 shows an electron micrograph of a cross section of a corner portion of the anode body after laser irradiation. In fig. 3, a valve metal (Ta) is present in a white portion, and a void is present in a black portion. It can be seen that the corner portion has a curved surface, and the surface layer X of the corner portion having the curved surface is densely formed. On the other hand, the inside of the surface layer X maintains a porous state.
Industrial applicability
The present invention can be applied to an electrolytic capacitor, and can be suitably applied to an electrolytic capacitor using a porous body for an anode body.
The present invention has been described with respect to presently preferred embodiments, but such disclosure should not be construed in a limiting sense. Various modifications and alterations will no doubt become apparent to those skilled in the art to which the present invention pertains upon reading the foregoing disclosure. Accordingly, the appended claims should be construed to include all such variations and modifications as do not depart from the true spirit and scope of the invention.
Description of the reference numerals
20: electrolytic capacitor
10: capacitor element
1: anode body
2: anode line
2a: first part
2b: second part
3: dielectric layer
4: solid electrolyte layer
5: cathode layer
5a: carbon layer
5b: metal paste layer
6: anode part
7: cathode part
8: conductive adhesive material
11: outer package
13: anode lead terminal
14: cathode lead terminal
14a: joint part
101A to 101C: major surface of anode body
102A to 102C: connection surface
103A: second connecting surface

Claims (15)

1. An electrolytic capacitor comprising a capacitor element, the capacitor element comprising:
a porous anode body;
a dielectric layer formed on a surface of the anode body; and
a solid electrolyte layer covering at least a portion of the dielectric layer,
the anode body has a plurality of major faces and corner portions,
the corner portion includes a plurality of edge portions and a vertex portion that join the plurality of main faces to each other,
the surface layer X of at least a part of the corner portion is denser than the surface layer Y of the main surface adjacent to the surface layer X,
porosity P in the surface layer X 1 Less than the porosity P in the surface layer Y 2 The surface layer X has the porosity P 1 A porosity P in the surface layer Y of 10% or less 2 Is more than 20 percent.
2. The electrolytic capacitor according to claim 1, wherein at least a part of the corner portion including the surface layer X has a curved shape or a chamfer shape.
3. The electrolytic capacitor according to claim 2, wherein the surface layer Y adjoins a portion having the curved surface shape or the chamfer shape in the corner portion.
4. The electrolytic capacitor according to claim 2, wherein the portion having the curved surface shape or the chamfer shape among the corner portions includes a portion having a radius of curvature R of 20 μm to 500 μm.
5. The electrolytic capacitor according to claim 2, wherein the corner portion has a portion having the curved surface shape or the chamfer shape including a portion having a radius of curvature R different from each other, and a difference between a maximum value and a minimum value of the radius of curvature different from each other is 350 μm or less.
6. The electrolytic capacitor according to claim 1, wherein the surface layer X and the surface layer Y have a porosity P that satisfies the porosity 2 Relative to the porosity P 1 Ratio P of 2 /P 1 A part of 5 or more.
7. The electrolytic capacitor according to any one of claims 1 to 5, wherein the solid electrolyte layer comprises a conductive polymer.
8. The electrolytic capacitor according to any one of claims 1 to 5, wherein the anode body is a sintered body of metal particles having a valve action.
9. A method for manufacturing an electrolytic capacitor, which is a method for manufacturing a solid electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the method comprising:
a step of preparing the anode body;
a step of covering at least a part of the anode body with the dielectric layer; and
a step of covering at least a part of the dielectric layer with the solid electrolyte layer,
the anode body has a plurality of main faces, and corner portions including a plurality of side portions and vertex portions connecting the plurality of main faces to each other,
the step of preparing the anode body includes irradiating at least a part of the corner portion with laser light so that a surface layer X of at least a part of the corner portion is thicker than a surface layer of the main surface adjacent to the surface layer XY densification, the porosity P in the surface layer X 1 Less than the porosity P in the surface layer Y 2 The surface layer X has the porosity P 1 A porosity P in the surface layer Y of 10% or less 2 And 20% or more.
10. The method for manufacturing an electrolytic capacitor according to claim 9, wherein at least a part of a main surface of the anode body adjacent to the corner portion is not irradiated with laser light.
11. The method for manufacturing an electrolytic capacitor according to claim 9 or 10, wherein the anode body is a sintered body of metal powder,
the irradiation of the laser is performed after sintering the metal powder.
12. A method for manufacturing an electrolytic capacitor, which is a method for manufacturing a solid electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the method comprising:
a step of preparing the anode body;
a step of covering at least a part of the anode body with the dielectric layer; and
a step of covering at least a part of the dielectric layer with the solid electrolyte layer,
the anode body has a plurality of main faces, and corner portions including side portions and vertex portions that join the plurality of main faces to each other,
the step of preparing the anode body includes causing dielectric particles to collide with at least a part of the corner portion so that a surface layer X of at least a part of the corner portion is denser than a surface layer Y of the main surface adjacent to the surface layer X, and the surface layer X has a porosity P 1 Less than the porosity P in the surface layer Y 2 The surface layer X has the porosity P 1 A portion of 10% or lessThe porosity P in the surface layer Y 2 And 20% or more.
13. The method for producing an electrolytic capacitor according to claim 12, wherein the average particle diameter of the dielectric particles is 0.1mm to 3mm.
14. A method for manufacturing a solid electrolytic capacitor including a capacitor element including a porous anode body, a dielectric layer formed on a surface of the anode body, and a solid electrolyte layer covering at least a part of the dielectric layer, the method comprising:
a step of preparing the anode body;
a step of covering at least a part of the anode body with the dielectric layer; and
a step of covering at least a part of the dielectric layer with the solid electrolyte layer,
the anode body has a plurality of main faces, and corner portions including side portions and vertex portions that join the plurality of main faces to each other,
the step of preparing the anode body includes vibrating the anode body together with a vibrating member so that a surface layer X of at least a part of the corner portion is denser than a surface layer Y of the main surface adjacent to the surface layer X, and a porosity P in the surface layer X 1 Less than the porosity P in the surface layer Y 2 The surface layer X has the porosity P 1 A porosity P in the surface layer Y of 10% or less 2 And 20% or more.
15. The manufacturing method of an electrolytic capacitor according to claim 14, wherein the vibration member is a screen.
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